CN1904003A - Nano-zirconium dioxide surface modified lubricating oil additive, lubricating oil and its preparation method - Google Patents
Nano-zirconium dioxide surface modified lubricating oil additive, lubricating oil and its preparation method Download PDFInfo
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- CN1904003A CN1904003A CN 200610069674 CN200610069674A CN1904003A CN 1904003 A CN1904003 A CN 1904003A CN 200610069674 CN200610069674 CN 200610069674 CN 200610069674 A CN200610069674 A CN 200610069674A CN 1904003 A CN1904003 A CN 1904003A
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Abstract
The present invention relates to a nano ZrO2 surface modified lubricating oil additive, lubricating oil in which said additive is added and its preparation method. Said lubricating oil additive is made up by mixing nano ZrO2 powder body in lubricating oil matrix, the described nano ZrO2 powder body is made up by combining an unimolecular layer of silane coupler on surface of amorphous nano ZrO2, the chemical structural general formula of the described silane coupler is Y-R-SiX3, and the weight percentage of nano ZrO2 powder body contained in lubricating oil is 0.01-0.5%.
Description
(1) technical field under
The present invention relates to a kind of lubricating oil additive, particularly a kind of nanometer ZrO
2The lubricating oil additive of surface modification, and the lubricating oil that adds above-mentioned lubricating oil additive, and its preparation method.
(2) background technology
The simple substance nano-powder material is as nano simple substance Cu, Sn, Pb etc.; Nano inorganic salt and sulfide-based powder are as LaF
3, molybdenumdisulphide, PbS etc.; Nanometer oxyhydroxide or oxide powder are as Mg (OH)
2, TiO
2, SiO
2Deng.Using above-mentioned nano material is added in the lubricating oil as slip additive and has obtained more achievement as tribology research, but many problems deserving of attention have also been found under study for action: after more active metal, basic oxide, intermediate oxide and the hydroxide nanoization, its reactive behavior significantly improves, easier and oxygen and acid-respons, and finally generate salt.Above-mentioned nanoparticle in use under sour gas and microcell produces in friction process high temperature action, is easy to nanoparticle finally is converted into inorganic salt.After this conversion realized, nanoparticle just can't be realized as the tribological property of slip additive.ZrO
2Be a kind of high temperature resistant, wear-resistant, corrosion resistant inorganic materials, its chemical stability height, water insoluble, hydrochloric acid, nitric acid and dilute sulphuric acid, it also is stable to sulfide, phosphide.Nanometer ZrO
2Have high tenacity and cold plasticity modification ability by a large amount of studies have shown that, can be used for preparing multiple increasing tougheness structural ceramics cutter, instrument, mould, bearing and advanced ceramic engine part etc.Therefore select ZrO
2Nanoparticle is researched and developed as the anti-friction antifriction lubricating oil additives, and bigger practical significance is arranged.
But ZrO
2The surface and the consistency of lubricating oil very poor, directly add nanometer ZrO in the lubricating oil
2, its stability, anti-attrition performance, self-healing properties do not reach requirement.
(3) summary of the invention
The present invention provides a kind of nanometer ZrO in order to overcome the deficiency of above technology
2The lubricating oil additive of surface modification, it is good to have with the consistency of lubricating oil, and good stability is set up the lubricant film of one deck selfreparing at surface of friction pair, plays the effect of anti-attrition, selfreparing.
Another object of the present invention is to provide the lubricating oil that adds above-mentioned lubricating oil additive.
Another object of the present invention is to provide above-mentioned preparation process lubricant oil additive.
The present invention realizes by following measure:
Nanometer ZrO of the present invention
2The lubricating oil additive of surface modification, its special feature is: mix nanometer ZrO in lubricating oil matrix
2Powder is made, described nanometer ZrO
2Powder is armorphous nano ZrO
2Surface recombination have a unimolecular layer silane coupling agent to make; The chemical structure of general formula of described silane coupling agent is expressed as: Y-R-SiX
3, wherein Y is vinyl, amino, epoxy group(ing), sulfydryl, methacryloxy or the urea groups that can react with organic compound; R has full closing or carbochain that key is closed in insatiable hunger; X is chlorine, methoxy or ethoxy.
Above-mentioned lubricating oil additive, described armorphous nano ZrO
2Particle diameter be 10-100nm.
Above-mentioned lubricating oil additive, described nanometer ZrO
2The weight percent of powder is 5-20%.
Above-mentioned lubricating oil additive, described being mixed under ultrasonic wave mixed.
A kind of lubricating oil that is added with above-mentioned lubricating oil additive, its special feature is: nanometer ZrO in lubricating oil
2The weight percent of powder is 0.01～0.5%.
Preparation process lubricant oil additive of the present invention, can adopt following steps:
(1) is 95% ethanol and 5% H by weight percentage
2O is made into alcohol-water solution, adds Glacial acetic acid, and adjusting PH is 4.5-5.5; Add silane coupling agent under stirring and make concentration reach 0.5%-5.0%, behind the hydrolysis 5min, promptly generate the hydrolyzate that contains Si-OH;
(2) the preparation particle diameter is the armorphous nano ZrO of 10-100nm
2
(3) the silane coupling agent alcohol-water solution for preparing is added in the ultrasonic grinding machine, opening device adds armorphous nano ZrO after 10 minutes
2, in 80 ℃ of ultrasonic grinding machines, stirring and pulverized 30 minutes, temperature is controlled at 80 ℃;
(4) in 100-120 ℃ baking oven dry 2 hours, porphyrize, surface-modified nano ZrO
2Powder;
(5) will lubricating oil adds in the ultrasonic grinding machine, and opening device adds surface-modified nano ZrO
2Powder was pulverized 2 hours in the ultrasonic grinding machine, made nanometer ZrO
2The lubricating oil additive of surface modification.
Preparation process lubricant oil additive of the present invention, also can adopt following steps:
(1) the organoalkoxysilane coupling agent is soluble in water, it is made into the solution of 0.5%-5.0%, add Glacial acetic acid PH is transferred to 5.5;
(2) the preparation particle diameter is the armorphous nano ZrO of 10-100nm
2
(3) the silane coupling agent aqueous solution for preparing is added in the ultrasonic grinding machine, opening device adds armorphous nano ZrO after 10 minutes
2, in 80 ℃ of ultrasonic grinding machines, stirring and pulverized 30 minutes, temperature is controlled at 80 ℃;
(4) in 100-120 ℃ baking oven dry 2 hours, porphyrize, surface-modified nano ZrO
2Powder;
(5) lubricating oil is added in the ultrasonic grinding machine, opening device adds surface-modified nano ZrO
2, in the ultrasonic grinding machine, stir and pulverized 2 hours, make nanometer ZrO
2The lubricating oil additive of surface modification.
The selection of 1 nano-lubricating material
ZrO
2Be a kind of high temperature resistant, wear-resistant, corrosion resistant inorganic materials, its chemical stability height, water insoluble, hydrochloric acid, nitric acid and dilute sulphuric acid, it also is stable to sulfide, phosphide.After with silane coupling agent its surface being carried out modification and handled, make it change the lipophilic surface into, thereby in lubricating oil, obtain single dispersion.Nanometer ZrO through surface modification treatment
2Particle is scattered in the lubricating oil, the ball shaped nano grain can in lubricant medium, play the effect of " molecule bearing "; When surface of friction pair reaches certain load and temperature, in case the metallic surface produces defective, because nanometer ZrO
2Particle is active high, will produce physics and chemisorption with the metallic surface, and the N atom in the particle surface silane also tends to be adsorbed onto the metallic surface, and forms inner complex, makes ZrO
2Particle is enriched in the cracks of metal surface place, thereby sets up the lubricant film of one deck selfreparing at surface of friction pair, can play the dynamically effect of selfreparing of antifriction antiwear and surface.
The selection of 2 stably dispersing modifiers
Nanoparticle requires to exist in the lubricating oil medium with single disperse phase in adding lubricating oil to the time.All right and wrong are oil loving because of most of inorganic nano-particle sub-surface, this just need carry out modification to its surface and handle, usually select some to contain the oil-soluble dispersion stabilizers such as organic compound of N, as dialkyl dithiophosphoric acid (DDP), stearic acid, oleic acid etc., wherein the part dispersion agent had both had dispersion stabilization, has tribological property again, as oleic acid, dialkyl dithiophosphoric acid (DDP) etc.Select silane coupling agent that the inorganic nano-particle surface modification is reached and on metal finishing, carried out number of research projects, and obtained a lot of achievements and application.Silane molecule has two kinds of different reactive groups, and Y-R-SiX can be used in its chemical structural formula
3Expression, in the formula: Y is the group that can react with organic compound, as amino, sulfydryl etc.; R has full closing or carbochain that key is closed in insatiable hunger, by it Y and Si atom is coupled together; X is the group that can be hydrolyzed and react and generate Si-OH, as alkoxyl group, acetoxyl group, halogen etc.X is the different active groups of two class response characteristics with Y.Therefore can be by silane in inorganic materials (as ZrO
2) and the interface of organic materials (as lubricating oil) between erect " molecule bridge ", the material of two kinds of different in kinds is coupled together.At present silane mainly contains theory of chemical bonds, physical adsorption theory and hydrogen bond in the theory of inorganics surface behavior and forms theory etc.And the theory of chemical bonds that B.Arkles proposes is considered to the most a kind of theory of approaching reality.This theory has proposed the four-step reaction model as shown in Figure 1: the Si-X base that 1. links to each other with silicon is hydrolyzed into Si-OH; 2. dehydrating condensation becomes to contain the oligosiloxane of Si-OH between the Si-OH; 3. Si-OH in the oligopolymer and the OH on the substrate surface form hydrogen bond; 4. follow dehydration reaction in the process that is heating and curing and form covalent linkage with base material.Inorganic through silane treatment (as ZrO
2) when nanoparticle was dispersed in the lubricating oil, because Y-R-Si-O is coated on nanoparticle surface, silane coupling agent did not have avidity mutually and is difficult to play between the compatible interface effect of " emulsifying agent " at two.Silane coupling agent also can be used for the protection of metal or alloy effectively, because silane coupling agent can form trialkylated silanol after hydrolysis, can interreaction become the crosslinked fine and close netted hydrophobic membrane of one deck between the alcoholic extract hydroxyl group, because there is the organo-functional group that can react with organism on this film surface, therefore sticking power can improve greatly, anticorrosive, friction resistant, shock proof ability also improve thereupon.Therefore, select silane coupling agent as dispersion stabilizer to inorganic nano-particle (as ZrO
2) carry out surface treatment research, correct as treatment process, can in lubricating oil, obtain the nanoparticle of single disperse phase.3ZrO
2The analysis of nanoparticle " molecule bearing " mechanism of action:
Nanoparticle is the effect that has realized " molecule bearing " because of nanoparticle in friction process to the improvement of antifriction performance, and model as shown in Figure 2.Realize the condition that " molecule bearing " mechanism should satisfy: 1. nanoparticle should be spheroidal particle, preferably exists with single disperse phase in lubricating oil; 2. the surface of friction pair roughness levels is suitable with nano particle diameter; 3. nanoparticle will have enough rigidity, and size distribution is narrower; 4. friction pair has certain rigid, and must be in contact with one another (only just can have this situation when boundary lubrication and mixed lubrication, concurrent looks is to motion); 5. suitably low load and sliding velocity will be arranged.Amorphous ZrO
2Nanoparticle is in preparation process, because of the presoma ZrO (OH) to it
2The temperature of carrying out roasting is 250～430 ℃.Therefore, amorphous ZrO
2The surface topography of nanoparticle is based on spheroidal particle, and agglomeration is less, and there is a large amount of hydrogen bond hydroxyls in the surface, and this surface properties makes amorphous ZrO
2Nanoparticle can carry out surface modification with silane coupling agent, changes oil loving nanoparticle into, obtains single disperse phase in lubricating oil.The nano-solid of energy realization " molecule bearing " effect is lubricated just to become a kind of good selection, not only can realize lubricating, even can realize super lubricated.
ZrO after 4 modifications
2Nanoparticle frictional wear selfreparing mechanism is resolved
In friction process, in order to make surface of friction pair because fricative micro-damage and tiny crack obtain dynamic compensation and reparation, thus the work-ing life of prolonged mechanical and economical with materials consumption, the slip additive that preparation has self-repair function is a ultimate aim.By in lubricating oil, adding nano material, set up one deck selfreparing lubricant film at surface of friction pair, for zero wearing and tearing and the dynamic selfreparing of original position provide a practicable approach.Utilize fricative mechanical friction, tribo-chemistry, friction-electrochemical action; friction pair and exchange of slip additive generate energy and exchange of substance; thereby on surface of friction pair, form metal, metal oxide protective membrane; organic poly-and thing film; physics or chemisorbed film etc.; with the attrition and attack of friction compensation secondary surface, form the wearing and tearing self-repair effect.Nanometer ZrO
2Be intermediate oxide, it at high temperature can form sosoloid with many metal oxides, can effectively improve the wear resistance of metallic substance surface of friction pair.As the nanometer ZrO that carries out surface modification treatment through silane coupling agent
2After particle was scattered in the lubricating oil, when load that acquires a certain degree when surface of friction pair and temperature, in case the metallic surface produces defective, its fault location was the higher zone of energy, this moment nanometer ZrO
2N atom in the silane of particle surface tends to be adsorbed onto the metallic surface, and forms inner complex, makes ZrO
2Particle is enriched in the cracks of metal surface place, and reaction model as shown in Figure 3.Thereby set up the lubricant film of one deck selfreparing at surface of friction pair, played the effect of antifriction antiwear.
5 theoretical analysises
Amorphous ZrO
2Nanoparticle surface has abundant hydroxyl (OH); And silane coupling agent (chemical structural formula is: Y-R-SiX
3), wherein Y can generate covalent bonds with organism (lubricating oil) etc.; The other end X is the reaction and generate the group of Si-OH of can being hydrolyzed, it can with amorphous ZrO
2The hydroxyl on surface covers, absorption and chemical bonding effect.Have only as itself and amorphous ZrO
2Chemical bonding takes place and does the time spent in the surface, and best modified effect is just arranged.This modifying process as shown in Figure 4.At first silane coupling agent is mixed with the certain density aqueous solution, allows its hydrolysis, then be hydrolyzed into Si-OH, in water, form oligopolymer, principle such as Fig. 4 (a) with the Si-X base that Si links; Second step is with solution of silane after the hydrolysis and amorphous ZrO
2Nanoparticle, high speed whip modified is handled under certain temperature and pressure condition, principle such as Fig. 4 (b), Si-OH in modifying process in the oligopolymer and ZrO
2The last OH on surface forms hydrogen bond, principle such as Fig. 4 (c); In the 3rd step, the mixed solution thermal dehydration that modification is good is followed dehydration reaction oligopolymer siloxanes and ZrO in this process
2Form covalent bonds on the surface, formed the siloxanes coating layer, as Fig. 4 (d).
With the amorphous ZrO after the modification
2After nanoparticle added in the lubricating oil, this nanoparticle and lubricating oil will produce good affinity, thereby can make amorphous ZrO
2Nanoparticle reaches single dispersion in lubricating oil.In process of friction and wear, on the contacted surface of friction pair, just can form " molecule bearing " effect.Nanometer ZrO
2Be intermediate oxide, when load that acquires a certain degree when surface of friction pair and temperature, in case the metallic surface produces defective, its fault location is the higher zone of energy, nanometer ZrO
2Can form sosoloid with it; While nanometer ZrO
2N atom in the particle surface silane tends to be adsorbed onto the metallic surface, and forms inner complex, makes ZrO
2Particle is enriched in the cracks of metal surface place, thereby sets up the lubricant film of one deck selfreparing at surface of friction pair, plays the effect of antifriction antiwear.
Lubricating oil additive of the present invention, it is good to have with the consistency of lubricating oil, good stability.The lubricating oil of lubricating oil additive makes ZrO in the interpolation
2Particle is enriched in the cracks of metal surface place, thereby sets up the lubricant film of one deck selfreparing at surface of friction pair, has the good characteristics of anti-attrition and self-healing properties.Adopt preparation method of the present invention, its finished product dispersing property is good, good stability, and anti-wear and wear-resistant performance is good.
(4) description of drawings
Fig. 1 is silane reagent and inorganic material surface reaction model
Fig. 2 is the rolling resistance action model of super-smooth surface
Fig. 3 is the contingent reaction of silane and metallic surface
Fig. 4 is to nanometer ZrO with silane coupling agent
2The improving particle surface model
Fig. 5 is a lubricating oil moment of friction change curve behind 20# lubricating oil and the adding additive of the present invention
Fig. 6 is a steel ball mill spot pattern metallographic microanalysis photo
(a) 1# sample steel ball mill spot pattern * 100 (b) 2# sample steel ball mill spot pattern * 100 wherein
Figure 72 sample ring piece rub(bing)test moment of friction curve
The change curve of moment of friction during change curve (d) the 200N power of moment of friction during change curve (c) the 150N power of moment of friction during change curve (b) the 100N power of moment of friction during (a) 50N power wherein
Fig. 8 tests the surface energy spectrum analysis of back 1# sample ring piece
Fig. 9 tests the surface energy spectrum analysis of back 2# sample ring piece
(5) embodiment
Armorphous nano ZrO
2Preparation
Adopt sol-gel method to prepare armorphous nano ZrO
2Preparation armorphous nano ZrO
2Best preparation parameter as follows:
Preparation 0.5mol/L ZrOCl
2Solution adopts heating in water bath that its temperature is remained on about 60 ℃; The dispersion agent polyoxyethylene glycol of adding 0.5%, constant temperature slowly drip certain amount of ammonia water under stirring fast after about 15 minutes, the regulation system pH value is 9, obtains hydrogel; Hydrogel ageing in mother liquor was adopted the washed with de-ionized water precipitation after 3 hours, till chlorion is by wash clean, the vacuum filtration dehydration; Then precipitation is changed in the flask and to add a certain amount of propyl carbinol and carry out component distillation and remove residual water-content in the presoma, when temperature rises to 113 ℃, propyl carbinol comes to life, and refluxes one hour, this precursor is put into baking oven dried two hours down at 120 ℃; Calcined 2 hours down at 350 ℃, obtain armorphous nano ZrO
2, its median size is 70nm.
Silane coupling agent is to armorphous nano ZrO
2Modification (gordian technique)
Armorphous nano ZrO
2Particle surface exists a large amount of hydroxyls (OH); And silane coupling agent (chemical structural formula is: Y-R-SiX
3, wherein Y can combine with organism generation covalence keys such as (lubricating oil); The other end X is the reaction and generate the group of Si-OH of can being hydrolyzed, can with amorphous ZrO
2The hydroxyl on surface covers, adsorbs and produce chemical b `.Have only as itself and unformed ZrO
2The valence bond cooperation time spent takes place in the surface, and best modified effect is just arranged.
1) silane coupling agent alcohol-water solution facture
At first by the ethanol (EtOH) of wt95% and the H of wt5%
2O is made into alcohol-water solution, adds Glacial acetic acid (AcOH), and adjusting PH is 4.5-5.5.Add silane coupling agent under stirring and make concentration reach wt2%, behind the hydrolysis 5min, promptly generate the hydrolyzate that contains Si-OH.If use the amino-alkyl silicane coupling agent, then needn't add AcOH.But the alcohol-water solution facture is not suitable for the chlorosilane type coupling agent, the latter will be in alcohol solution polymerization reaction take place.When the trifunctional silane coupling agent solution that uses 2% concentration was handled, what obtain mostly was the thick coating of 3-8 molecule.
2) silane coupling agent aqueous solution facture
Earlier that the organoalkoxysilane coupling agent is soluble in water, it is made into the solution of 0.5%-2.0%.For the relatively poor silane of solvability, can in water, add 0.1% nonionic surface active agent in advance and be mixed with water miscible liquid, add AcOH again PH is transferred to 5.5.Because the stability of the silane coupling agent aqueous solution differs greatly, only can stability number hour as the simple alkylalkoxy silane aqueous solution, and ammonia hydrocarbon silane-water solution can be stablized several weeks.Because the solubility parameter of chain alkyl and phenyl silane is low, so can not use this method.During the preparation silane-water solution, need not to use deionized water, but can not use the water of fluoride ion.
3) realize ZrO with silane coupling agent
2Surface unimolecular layer modification
The shared reactive behavior of object being treated (matrix) unit specific surface area is counted out and the thickness of silane coupling agent covering surfaces is the key factor of the required coupling agent consumption of decision silica-basedization of matrix surface.Cover for obtaining unimolecular layer, need to measure earlier the Si-OH content of matrix.Known, the Si-OH number of most siliceous matrix is 4-12/μ m
2, thereby during uniform distribution, the 1mol silane coupling agent can cover about 7500m
2Matrix.Silane coupling agent with a plurality of hydrolysable group, owing to self condensation reaction, what will influence the accuracy of calculating.If use Y
3SiX handles matrix, then can obtain the unimolecular layer consistent with calculated value and cover.
The wettable area (WS) of silane coupling agent is meant that the solution of 1g silicon a heatable brick bed coupling agent can cover the area (m of matrix
2/ g).If with itself and the surface area values (m that contains silicon substrate
2/ g) association can calculate unimolecular layer and cover required silane coupling agent consumption.ZrO
2The surface forms unimolecular layer and covers required silane coupling agent consumption W (g) and ZrO
2Specific surface area Sw (the m of powder
2/ g) and quality be directly proportional, and with the wettable area WS (m of silane
2/ g) be inversely proportional to.Can get modification ZrO
2The calculating formula of the silane coupling agent consumption during powder is as follows:
With the KH-560 silane coupling agent is example, and its molecular formula is as follows:
Its molecular weight is: 236g/mol.
So realize nanometer ZrO
2When unimolecular layer covered M (g) powder, the silane coupling agent consumption was:
In the formula, Sw--is nanometer ZrO
2The quality of powder is recorded m than surface-area by the specific surface area instrument
2/ g; The 1mol silane coupling agent can cover about 7500m
2Matrix; The molecular weight of KH-560 silane coupling agent is: 236g/mol.
The silane coupling agent alcohol-water solution or the aqueous solution that prepare are added in the ultrasonic grinding machine (patent application people's patent of invention), and opening device adds unformed nanometer ZrO after 10 minutes
2(add-on is pressed following formula and calculated) powder stirs in 80 ℃ of ultrasonic grinding machines and pulverized 30 minutes, and temperature is controlled at 80 ℃.The effect of pulverizing in the ultrasonic grinding machine is the powder of reuniting to be opened to make all have silane coupling agent to cover (key problem in technology) on the individual particle.Dry 2 hours (100-120 ℃) in baking oven is chip solid drying is finished after, microwave 10 minutes in microwave oven then, and the removal residual water-content, porphyrize promptly obtains the good nanometer ZrO of modification
2Powder, its color white before by modification becomes coffee color.
The preparation of slip additive
According to the difference of lubricating oil working conditions, lubricating oil is divided into different models, and this additive is applicable to the lubricating oil of various models.
A certain amount of lubricating oil is added in the ultrasonic grinding machine, and opening device is then by the nanometer ZrO after the 10% adding modification that adds the quality of lubrication oil ratio
2Powder was pulverized 2 hours in the ultrasonic grinding machine, promptly made amorphous nanometer ZrO
2Slip additive.Pulverizing in the ultrasonic grinding machine is in order to open the nanometer ZrO of reunion
2Powder makes nanometer ZrO
2Particle reaches single dispersion (key problem in technology) in lubricating oil.In use by nanometer ZrO
2Powder quality accounts for 5/10000ths of lubricating oil add-on and prepares and get final product.
The preparation of lubricating oil 1:
The modified Nano ZrO that in 20# lubricating oil, adds 0.05% mass ratio
2Powder is prepared with above-mentioned technology.Carry out four ball frictional wear simultaneous tests.
Testing apparatus is vertical omnipotent friction wear testing machine, model: MMW-1, and test Billion Group in Jinan produces.Steel ball (Gcrl5, secondary steel ball, diameter 12.7mm, hardness 64-66HRC).
Test sample is 20# lubricating oil (1# sample), contain 0.05% nanometer ZrO
2The 20# lubricating oil of additive (2# sample of the present invention).Examination contrast index is that moment of friction changes, worn steel ball quality and mill spot morphology change.
The used test power of vertical omnipotent friction wear testing machine is 392N; Rotating speed is 1200r/min; Measuring Time is 30 minutes, and per minute writes down 1 secondary data.
1) moment of friction changes contrast
The results are shown in shown in Figure 5.As shown in Figure 5, under the same experimental conditions parameter, contain 0.05% modified Nano ZrO
2The moment of friction of the 20# lubricating oil of particle additive (2# sample) comparing with 20# lubricating oil (1# sample) reduces a lot, and this illustrates with nanometer ZrO
2Particle can play certain antifriction function really as lubricating oil additive.
2) wearing and tearing quality contrast
Worn steel ball quality change before and after the test is shown in Table 1.
The worn steel ball mass analysis table of 2 groups of tests of table 1
| Grouping | Quality (g) before the mill | Mill back quality (g) | Quality wearing and tearing (g) |
| The 1# sample | 33.5105 | 33.5103 | 0.0002 |
| The 2# sample | 33.4190 | 33.4230 | -0.0040 |
As can be seen from Table 1, after the 1# sample was tested, steel ball quality reduced 0.0002g, and after 2# tested, steel ball quality increased to some extent, promptly negative wearing and tearing.Reason is that nano particle has higher diffusibility and self-diffusion ability in friction process, form pervious course or diffusion layer with splendid abrasion resistance in the metallic surface, nano particle additive has formed stable " trisome " to the filling effect of friction convex-concave surface and the friction chemical reaction on surface, possessed superior anti-wear effect, played certain wear-resistant effect.
3) steel ball mill spot pattern contrast
As shown in Figure 6, after rub(bing)test, the wear scar diameter of 1# sample steel ball is 708.1 μ m, and the wear scar diameter of 2# sample steel ball reduces a lot, is respectively 597.7 μ m.This is because nanometer ZrO
2Particle may deposit rapidly at surface of friction pair, form a kind of protective membrane, and this selfreparing film can exist with solid-state after friction; repair the friction surface indenture; reduced the roughness of surface of friction pair, played certain wear-resistant effect, thereby reduced wear scar diameter.
The preparation of lubricating oil 2:
The modified Nano ZrO that in 20# lubricating oil, adds 0.05% mass ratio
2Powder is prepared with above-mentioned technology.Carry out standard ring piece frictional wear simultaneous test.
Testing apparatus is the same, and going up sample in the test of ring piece is big thrust circle, and No. 45 steel are quenched into 45-50HRC, and external diameter is 50mm, and internal diameter is 42mm, and thickness is 5mm; Following sample is big test ring, and No. 45 steel are quenched into 44-46HRC, and external diameter is 54mm, and internal diameter is 38mm, and thickness is 10mm.Testing initial load is 50N, and the back increases 50N every 10min, until 200N finishes, total time on test is 40min; Test speed is 1200r/min, room temperature.After the off-test, sample cleans 30min in ultrasonic cleaner, and soak in acetone soln the back, fully removes specimen surface impurity.
Test sample is 20# lubricating oil (1# sample), contain 0.05% nanometer ZrO
2The 20# lubricating oil of powder (2# sample of the present invention).Examination contrast index is that moment of friction changes, ring piece surface chemistry analysis of components.
1) moment of friction changes contrast
Ring piece rub(bing)test moment of friction change curve as shown in Figure 7.As shown in Figure 7, under four pressure, contain nanometer ZrO
2The sample ratio of the additive not moment of friction of additive lubricating oil all has reducing of certain amplitude, has played antifriction function, from holistic approach as can be seen, contains 0.05% nanometer ZrO
2The friction reducing effect that the lubricating oil of additive produces is best.
2) ring piece surface chemistry analysis of components
After the test, Fig. 8, shown in Figure 9 is seen in the X-ray energy spectrum analysis that 1# and 2# sample ring piece friction surface are carried out.
Ferro element is only contained on the ring piece surface of 1# sample as shown in Figure 8, and 2# sample ring piece surface has also increased O, Zr and Si element in addition as shown in Figure 9, and there is nanometer ZrO on the surface of this explanation ring piece
2Existence, verified nanometer ZrO just
2Particle has played good friction self-repair function to the surface of ring piece in greasing, repair the friction surface indenture, thereby played the antiwear and antifriction effect.And the existence of element silicon is because nanometer ZrO
2Silane coupling agent is introduced in modifying process.
Claims (7)
1. nanometer ZrO
2The lubricating oil additive of surface modification is characterized in that: mix nanometer ZrO in lubricating oil matrix
2Powder is made, described nanometer ZrO
2Powder is armorphous nano ZrO
2Surface recombination have a unimolecular layer silane coupling agent to make; The chemical structure of general formula of described silane coupling agent is expressed as: Y-R-SiX
3, wherein Y is vinyl, amino, epoxy group(ing), sulfydryl, methacryloxy or the urea groups that can react with organic compound; R has full closing or carbochain that key is closed in insatiable hunger; X is chlorine, methoxy or ethoxy.
2. lubricating oil additive according to claim 1 is characterized in that: described armorphous nano ZrO
2Particle diameter be 10-100nm.
3. lubricating oil additive according to claim 1 is characterized in that: described nanometer ZrO
2The weight percent of powder is 5-20%.
4. lubricating oil additive according to claim 1 is characterized in that: described being mixed under ultrasonic wave mixed.
5. a lubricating oil that adds the described lubricating oil additive of claim 1 is characterized in that: nanometer ZrO in lubricating oil
2The weight percent of powder is 0.01～0.5%.
6. described preparation process lubricant oil additive of claim 1 is characterized in that: adopt following following steps:
(1) is 95% ethanol and 5% H by weight percentage
2O is made into alcohol-water solution, adds Glacial acetic acid, and adjusting PH is 4.5-5.5; Add silane coupling agent under stirring and make concentration reach 0.5%-5.0%, behind the hydrolysis 5min, promptly generate the hydrolyzate that contains Si-OH;
(2) the preparation particle diameter is the armorphous nano ZrO of 10-100nm
2
(3) the silane coupling agent alcohol-water solution for preparing is added in the ultrasonic grinding machine, opening device adds armorphous nano ZrO after 10 minutes
2, in 80 ℃ of ultrasonic grinding machines, stirring and pulverized 30 minutes, temperature is controlled at 80 ℃;
(4) in 100-120 ℃ baking oven dry 2 hours, porphyrize, surface-modified nano ZrO
2Powder;
(5) will lubricating oil adds in the ultrasonic grinding machine, and opening device adds surface-modified nano ZrO
2Powder was pulverized 2 hours in the ultrasonic grinding machine, made nanometer ZrO
2The lubricating oil additive of surface modification.
7. described preparation process lubricant oil additive of claim 1 is characterized in that: adopt following steps:
(1) the organoalkoxysilane coupling agent is soluble in water, it is made into the solution of 0.5%-5.0%, add Glacial acetic acid PH is transferred to 5.5;
(2) the preparation particle diameter is the armorphous nano ZrO of 10-100nm
2
(3) the silane coupling agent aqueous solution for preparing is added in the ultrasonic grinding machine, opening device adds armorphous nano ZrO after 10 minutes
2, in 80 ℃ of ultrasonic grinding machines, stirring and pulverized 30 minutes, temperature is controlled at 80 ℃;
(4) in 100-120 ℃ baking oven dry 2 hours, porphyrize, surface-modified nano ZrO
2Powder;
(6) lubricating oil is added in the ultrasonic grinding machine, opening device adds surface-modified nano ZrO
2, in the ultrasonic grinding machine, stir and pulverized 2 hours, make nanometer ZrO
2The lubricating oil additive of surface modification.
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| CNB2006100696742A CN100537729C (en) | 2006-08-07 | 2006-08-07 | Nanometer ZrO 2The lubricating oil additive of surface modification, lubricating oil and preparation method thereof |
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|---|---|
| CN100537729C (en) | 2009-09-09 |
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